Dye composition containing indophenol for keratinous fibers and method using the same

ABSTRACT

Hair dye and hair setting lotion compositions contain an indophenol of the formula   WHEREIN R1, R2, R3 and R4 represent hydrogen, halogen, lower alkoxy and lower alkyl with at least one of R1, R2, R3 and R4 being halogen and the alkaline salts of said indophenol.

United States Patent [191 Kalopissis et al.

[451 July 15,1975

[73] Assignee: Societe Anonyme dite: LOreal, Paris, France [22] Filed:July 27, 1972 [21] Appl. No.: 275,463

Related US. Application Data [63] Continuation-in-part of Ser. No.l00,433, Dec. 21, 1970, abandoned, which is a continuation-in-part ofSer. No. 49,905, June 25, l970, abandoned.

[30] Foreign Application Priority Data June 25, 1969 Luxembourg 58954July 30, 1971 Luxembourg 63641 [52] US. Cl. 8/10; 8/101; 8/102; 8/11;260/386 N; 424/DIG. 2; 424/71 [51] Int. Cl D06p 3/04 [58] Field ofSearch 8/l0.2, 11; 260/386 N; 424/70 [56] References Cited UNlTED STATESPATENTS 3,730,677 5/1973 Kalopissis et al. 8/l0.2

FOREIGN PATENTS OR APPLICATIONS 339,044 9/l904 France 8/102 X 157,288l0/l902 Germany 8/10.2 X 1,078,717 3/1960 Germany 8/102 X 773,794 5/1957United Kingdom 8/10.2

OTHER PUBLICATIONS Lange American Perfumer and Cosmetics, 6/1965, Vol.80, No. 6, pp. 33 to 37.

Primary Examiner-Albert T. Meyers Assistant Examiner-Dale R. Ore

Attorney, Agent, or Firm-Cushman, Darby & Cushman [57 ABSTRACT l-lairdye and hair setting lotion compositions contain an indophenol of theformula wherein R,, R R and R represent hydrogen, halogen, lower alkoxyand lower alkyl with at least one of R R R and R being halogen and thealkaline salts of said indophenol.

7 Claims, No Drawings DYE COMPOSITION CONTAINING INDOPI-IENOL FORKERATINOUS FIBERS AND METHOD USING THE SAME This application is acontinuation-in-part of our application Ser. No. 100,433, filed Dec. 21,1970, now abandoned which, in turn is a continuation-in-part of ourapplication Ser. No. 49,905 filed June 25, 1970, now abandoned.

The present invention relates to a novel dye composition for keratinousfibers, in particular human hair, comprising a solution in a solventselected from the group consisting of water and an aqueous solution of alower alkanol of an indophenol of the formula wherein R R R and R eachindependently represent a member selected from the group consisting ofhydrogen, halogen, such as chlorine and bromine, lower alkoxy containing1-4 carbon atoms and lower alkyl containing from 1 to 4 carbon atomswith the proviso that at least one of R R R and R is halogen; or to analkaline salt of said indophenol such as its ammonium, sodium orpotassium salt, and to the tautomers thereof.

The indophenols used in the dye compositions of the present inventioncan be prepared by condensing in a known manner a paraaminophenol of theformula:

Ho{ NH I on a phenol of the formula:

wherein R,, R R and R have the meanings given above. This condensationreaction is performed in an aqueous alkaline medium having, generally, apH of about 8 to 12, preferably about 10.5 to 1 l, at a temperaturebetween and 40C and in the presence of an oxidizing agent such as air,hydrogen peroxide, potassium or ammonium persulfate, sodium hypochloriteor potassium ferricyanide.

The mole ratio of phenol to paraaminophenol ranges between about 0.5:1to 2:1 and is preferably 1:1. The amount of oxidizing agent canvarybetween about 1 to times the stoichiometric quantity for oxidizing theparaaminophenol to the corresponding quinone-imine. This amount ispreferably equivalent to 1 mol of persulfate or 2 moles of ferricyanideper 1 mol of paraaminophenol.

Alternatively, the said indophenol can be prepared by condensing aparaaminophenol of the formula E 1 HO in; d

on a phenol of the formula:

wherein R R R and R have the meanings given above under essentially thesame conditions outlined immediately above.

The above indophenols can also be prepared by condensing a chlorinatedquinone-imine of the formula on a phenol of the formula:

wherein R R R and R have the meanings given above in an alkaline mediumat a pH of about 10 to 12 and at a temperature of about 1040C. The moleratio of chlorinated quinone-imine to phenol is preferable 1:1.

As an alternative to this condensation reaction the chlorinatedquinone-imine can be of the formulaN-[(4-hydroxy-2-chloro)phenyl]-3-methyl benzoquinoneimine (newcompound),

N-[(4'-hydroxy-2-chloro)phenyl]-3-chloro benzoquinoneimine (newcompound),

N-[ (4 -hydrox )phenyl ]-3-chloro benzoquinoneimine,

N-[(4-hydroxy-3-chloro)phenyl]-3-chl0ro benzoquinoneimine (newcompound),

N-[(4'-hydroxy-3'-chloro)phenyl]-2-chloro benzoquinoneimine (newcompound),

N-[(4-hydroxy-3,5'-dibromo)phenyl] benzoquinoneimine,

N-[(4'-hydroxy-3,5-dibromo)phenyl] Z-methyl benzoquinoneimine,

N-[(4-hydroxy-3,5'-dichloro)phenyl]2-methyl benzoquinoneimine,

N-[(4-hydroxy-3',5-dichloro)phenyl]-3 methyl benzoquinoneimine,

N-[(4-hydroxy-3,5'-dibromo)phenyl]-2,6-dimethyl benzoquinoneimine andN-[(4-hydroxy-3'chloro)phenyl]-2,6-di benzoquinoneimine.

The new halogenated indophenols mentioned above have the general formula(I) in which R and/or R represents a methyl or tertiary butyl radical ora hydrogen or chlorine atom, and/or R and/or R represents a chlorine,bromine or hydrogen atom.

The dye composition of the invention can contain only the indophenols offormula l, in which case it imparts to the fibers treated therewith afrequently pearly appearance and shades of a great variety, which shadesare very luminous and rich in glints and include violets, mauves, blues,blue greens, orange yellows, pinks ranging from violet pink to salmonpink, and golden or copper blonds, ash beiges, pink beiges or silvergrays.

However, the dye composition of this invention can also of courseinclude one or more conventional hair dyes, for examples, other directdyes, such as nitro dyes of the benzene series, azo dyes, anthraquinonedyes, oxazines, azines, indoanilines, indamines or other indophenols,such as those set forth in Ser. No. 100,433.

The concentration of the indophenols of this invention in the dyecomposition of the present invention can range from about 0.002 to 2percent by weight, preferably about 0.005 and 0.5 percent by weight.

The pH of the dye composition according to the present invention canvary between 4 and l l, and prefera bly between about 5 and 10. Toregulate this pH at the desired value, conventional pH regulators suchas an t-butyl alkalizing agent including ammonia or an amine such asmono-, di or triethanolamine and an acidifying agent such as aceticacid, lactic acid or phosphoric acid can be used.

The compositions according to the invention can be in the form of purelyaqueous solution of said indophenol, especially when the indophenol ispresent in the form of an alkaline salt thereof. However, thecomposition of the present invention can also include a lower alkanolsuch as ethanol or isopropanol, in amounts of about 20-70 weight percentor a glycol, such as propyleneglycol or butylglycol, in an amount of lto 6% by weight. These alkanols and glycols facilitate solubilizing saidindophenols.

Additionally, the dye composition of the present invention can alsoinclude various conventional components usually used in capillarycosmetics, for example, wetting agents, dispersing agents, penetratingagents, swelling agents, thickeners or perfumes. Further, it can beprovided in the form of creams or gels or it can be provided in the formof a sprayable aerosol, packaged under pressure in conventional aerosolcontainers.

Keratin fibers, in particular, human hair, can be dyed with the dyecomposition of this invention in any conventional manner and usually byapplying said composition on the fibers to be dyed and permitting thedye composition to remain in contact with the fibers for about 3 to 30minutes. Thereafter, the treated fibers are rinsed and, if desired, evenwashed before drying the same.

As another embodiment of a cosmetic composition of the presentinvention, there is provided a capillary hair-setting lotion comprisingan indophenol as defined above dissolved in an aqueous lower alkanolsolution; together with a conventional wateror lower alkanolsolublecosmetic resin such as polyvinylpyrrolidone having a molecular weightranging from about 10,000 to 200,000, copolymer of crotonic acid-vinylacetate, said copolymer having a molecular weight ranging from about10,000 to 70,000, copolymer of vinylpyrrolidone and vinyl acetatewherein the ratio of VP to VA ranges between 50-70:50-30, said copolymerhaving a molecular weight ranging from about 30,000 to 200,000 andmaleic anhydride-butyl vinyl ether copolymer, a 1% solution of which inmethylethyl ketone has a viscosity of 0. l-3.5 cps at 25C. Obviously,other conventional film-forming cosmetic resins can also be employed.These resins are used in amounts of about 1 to 3 percent by weight ofthe hair-setting lotion composition.

The alcohols suitable for the preparation of the hairsetting lotionsaccording to the invention are low molecular weight alkanols, such asethanol or isopropanol which are present in amounts of about 20 to byweight of the total hair-setting lotion composition.

The pH of the hair-setting lotion composition of this inventiongenerally ranges between about 5-8 and can be regulated to the desiredvalue with the alkalizing or acidifying agents set forth above.

The hair-setting lotions of the present invention im- .part to hair agreat variety of hues, as described above,

which are characterized by a pearly or iridescent appearance and a greatrichness of glints. These hairsetting lotions are usually employed byapplication to wet hair, previously washed and rinsed, followed byrolling the hair up on curlers and drying the hair.

The following examples are given to illustrate the present invention.The temperatures appearing in these examples are expressed in degreecentigrade and, unless otherwise specifically stated, all parts andpercentages are by weight.

EXAMPLE 1 N-[(4'-hydroxy-2-chloro)phenyl]-2,6-dimethyl benzoquinoneimineis prepared as follows:

Cll

0.35 mole (42.7 g) of 2,6-dimethyl phenol is dissolved in 800 cc ofwaterto which have been added 600 cc of acetone and 530 cc of ammonia at22Be. To this resulting solution, cooled in ice, there are addedgradually and simultaneously by means of a double funnel with stirring,on the one hand, 0.35 mole (50.2 g) of 3-chloro-4-amino phenol dissolvedin 800 cc of water to which have been added 90 cc of hydrochloric acid(11 1.19), and on the other hand, 0.7 mole (160 g) of ammoniumpersulfate dissolved in 900 cc of water. When the addition is completed,the stirring is continued for minutes. The above indophenol which hasprecipitated is filtered and washed with aqueous acetone solution. Afterrecrystallization in an acetonewater mixture the above indophenolexhibits a melting point of 195C. Molecular weight calculated for C HNClO 261.5 Molecular weight found by potentiometric determination inacetic acid by perchloric acid 260.

Calculated for washed with a 20% aqueous acetone solution. Afterrecrystallization in an acetone-water mixture and drying under a vacuum,the above indophenol exhibits a melting point of 182C.

Molecular weight calculated for C H NCION-[(4-hydroxy-3'-chloro)phenyl]-2,5-dimethyl benzoquinoneimine isprepared as follows:

There are dissolved, on the one hand, 0.01 mole (1.80 g) of 2-chloro4-amino phenol hydrochloride and, on the other hand, 0.01 mole (1.22 g)of 2,5- dimethyl phenol in 25 cc of water to which have been added 15 ccof acetone and 6 cc of ammonia at 22Be. To this resulting solution,previously cooled in ice, there is gradually added, with stirring, 0.02mole (4.60 g) of ammonium persulfate dissolved in 15 cc of water. Whenthe addition is completed, stirring is continued for 15 minutes. Theabove indophenol which has pre- Analysls CHHIZNOZCI Found cipitated, isfiltered,- washed with a 30% aqueous ace- C% 6424 6426 6439 tonesolution and dried under vacuum. The above indo- H% 4.59 4.63 4.71phenol exhibits a melting point of 167 C. N74 5.35 5.46 5.39 C17: 136113.67 v 13.54

Molecular weight calculated for C H NClO 261.5 EXAMPLE 2 Molecularweight found by potentiometric determination in dimethylformamide by 0.1N TBA 264. N-[ (4-hydroxy-2'-chloro) phenyl]-2,5-d1methyl I Calculatedfor benzoquinoneimine is prepared as follows: Analys's clHzNcmz Found C%64.24 64.53 64.28 H% 4.59 4.44 4.57 N% 5.35 5.46 5.40

EXAMPLE 4 0.04 mole (4.9 g) of 2,5-dimethyl phenol is dissolved in asolution made up of 20 cc of water, 50 cc of acetone and 40 cc ofammonia at 22Be. To this resulting solution, cooled in ice, there areadded gradually, with stirring and simultaneously by means of a doublefunnel, on the one hand 0.04 mole (5.72 g) of 3-chloro-4- amino phenoldissolved in 80 cc of water to which have been added 10 cc ofhydrochloric acid (d 1.19), and on the other hand, 0.08 mole (18.24 g)of ammonium p'ersulfate in cc of water. When the addition is completed,stirring is continued for 10 minutes. The above indophenol which hasprecipitated is then filtered andN-[(4'-hydroxy-3-chloro)phenyl]-2,3-dimethyl benzoquinoneimine ispreparedas follows:

CH C

' Molecular weight calculated for C H NCIO 261.5 Molecular weight foundby potentiometric determination in dimethylforrnamide by 0.1 N TBA 260.

Calculated for Analysis C, H NClO Found EXAMPLE 5 N-[(4'-hydroxy-2'-chloro)phenyl]-2,3-dimethyl benzoquinoneimine is preparedas follows:

On the one hand, 0.01 mole (1.43 g) of 3-chloro-4- amino phenol and, onthe other hand, 0.01 mole (1.22 g) of 2,3-dimethyl phenol are dissolvedin 25 cc of water, 25 cc of acetone and 6 cc of ammonia at 22Be. To thisresulting solution, previously cooled in ice, there is gradually added,with stirring, 0.02 mole (4.60 g) of ammonium persulfate dissolved in ccof water.

in accordance with this alternate procedure exhibits a melting point of230C and there is not observed a drop in its melting point when used inmixture with the indophenol prepared in Example 5.

EXAMPLE 7 N-[(4'-hydroxy-3-chloro)phenyl]2,6-dimethyl benzoquinoneimineis prepared as follows:

0.15 mole (18.3 g) of 2,6-dimethyl phenol is dissolved in 375 cc ofwater to which have been added 225 cc of ammonia at 22Be. To thisresulting solution, cooled in ice, there. are gradually added, withstirring and simultaneously by means of a double funnel, on the onehand, 0.15 mole (27 g) of 2-chloro-4-amino phenol hydrochloride in 300cc of water and, on the other hand, 0.3 mole (98.7 g) of potassiumferricyanide in 300 cc of water. When the addition is completed,stirring is continued for 15 minutes. 25 g of the above indophenol, inthe form of its ammonium salt precipitate and are filtered, washed witha little ammoniacal liquor and dried.

These 25 g of ammonium salt are then introduced into 90 cc of ethanol towhich have been added 2.4 cc of acetic acid, with stirring. After 15minutes of stirring, 19 g of the above indophenol, which melts at 164,precipitate and are filtered, washed with a little ethanol and driedunder vacuum.

When the addition is completed, stirring is continued Molecular weightcalculated for C .,H N C1O 261.5 for 10 minutes. The above indophenol,which has pre- 40 F f l l by minatron 1n acetlc acid by perchloric acid264 cipitated 1s filtered and washed with a 50% aqueous acalcuiated fetone solution. After recrystallization in a dimethylfor- AnalysiS u m zFound mamlde-water mlxture and d rymg under vacuum, the (3% 6424 64146418 product (2.5 g) melts at 230 C. 11% 4.59 4.61 4.60 N% 5.35 5.255.32 C1% 13.61 13.58 13.49

Molecular product calculated for C I-l 12NC|O2 261.5 Molecular weightfound by potentiometric determination in dimethylformamide by 0.1 N TBA263. EXAMPLE 8 Calculated for I Analysis c,,,1-1,,1-1(:1o Fou N-[(4-hydroxy-2 -ch1oro )phenyl]-3-methyl benzoquinoneimine is prepared asfollows: C% 64.24 64.14 64.30 11% 4.59 4.66 4.62 N% 5.35 5.27 5.29 Cl CHHO N 0 EXAMPLE 6 N-[(4-hydroxy-2-chloro)phenyl]-2,3-dimethyl ben-Zoquinoneimine is prepared in an alternative process as follows:

On the one hand, 0.01 mole (1.76 g) of 3-chloro quinonechloroimide isdissolved in 15 cc of acetone and, on the other hand, 0.01 mole (1.22 g)of 2,3- dimethyl phenol is dissolved in 10 cc of acetone and 10 cc of anormal soda solution. These two resulting solutions, previously cooledto 0, are then mixed and the reaction mixture is left at thistemperature for 30 minutes. The above indophenol which precipitates isthen filtered, washed with a 50 percent aqueous acetone solution anddried under vacuum. The indophenol made On the one hand, 0.02 mole (3.52g) of 3-chloro quinonechloroimide is dissolved in 25 cc of acetone and,on the other hand, 0.02 mole (2.16 g) of metacresol is dissolved in 20cc of a 0.5 N soda solution. To the metacresol solution, previouslycooled to 0, there is gradually added the acetone solution of 3-chloroquinonechloroimide. When the addition is completed, the reaction mediumrapidly takes on a royal blue coloring. Then 5 cc of a 4 N soda solutionis added to it, thereby precipitating the above indophenol in the formof its crystallized sodium salt. This precipitate is filtered, thenwashed first with a very slight amount of salt Molecular weightcalculated for c n no ci Molecular weight found by potentiometricdetermination in dimethylformamide with 0.1 N solution oftetra-n-butylammonium (TBA) hydroxide in a methanol-isopropanol mixtureCalculated for Analysis Found EXAMPLE 9N-[(4'-hydroxy-2'-chloro)phenyl]-3-chloro zoquinoneimine is prepared asfollows:

it 01 no- 1.36:

On the one hand, 0.02 mole (3.52 g) of 3-chloro quinone chloroimide isdissloved in cc of acetone and, on the other hand, 0.02 mole (2.57 g) ofmetachlorophenol is dissolved in cc ofa 0.5 N soda solution. To the sodasolution of metachlorophenol, previously cooled to 0, there is graduallyadded the acetone solution of 3-chloro quinonechloroimide. When theaddition is completed, the reaction mixture rapidly takes on a bluecoloring. Then, 5 cc ofa 4 N soda solution is immediately added to it,thereby precipitating the above indophenol in the form of itscrystallized sodium salt. This salt is then filtered, washed withacetone and dried under vacuum. This salt is then dissolved in water andafter acidification of the resulting solution with acetic acid, theabove indophenol which has precipitated is filtered, washed with waterand dried under vacuum. It is chromatographically pure and melts at170C.

ben-

Molecular weight calculated for C, H-,NO Cl 268 Molecular weight foundby pctentiometric determination in dimethylformamide with a 0.1 Ntetra-nbutylammonium (TBA) hydroxide in a methanol/isopropanol mixture272 EXAMPLE l0 '-hydroxy)phenyl]-3-chloro mine is prepared as follows:

benzoquinoneihand, 0.01 mole (1.45 g) of paraaminophenol hydrochloride,and on the other hand, 50 cc of a solution of sodium hypochlorite (d1.05) at French chlorometric 10. When the addition is completed, thereaction mixture is at 5. The sodium salt of the above indophenol whichhas precipitated is immediately filtered, washed with acetone and driedunder vacuum, yielding 0.84 g of this salt. Then this salt is dissolvedin water. After acidification of the resulting solution with aceticacid, the above indophenol which has precipitated is filtered, washedwith water and dried under vacuum. It is chromatographically pure andmelts at 168C.

zoquinoneimine is prepared as follows:

On the one hand, 0.01 mole (1.76 g) of 3-chloro quinonechloroimide isdissolved in 10 cc of acetone and, on the other hand, 0.01 mole (1.28 g)of orthochlorophenol is dissolved in 10 cc of acetone and 12 cc of anormal soda solution. To the acetone solution of 3-chloroquinonechloroimide, previously cooled to 0, there is gradually added,with stirring, the soda solution of orthochlorophenol. The stirring iscontinued for 30 minutes and the reaction medium is then saturated withsodium chloride. The sodium salt of the above indophenol in crystallizedform is then filtered and washed with acetone, yielding 2.5 g of dryproduct which is chromatographically pure. This salt is then dissolvedin water. After acidification of the resulting solution with aceticacid, the above indophenol which has precipitated is filtered, washedwith water and recrystallized with an acetone-water mixture. Afterdrying under vacuum, it exhibits a melting point of 192C.

Molecular weight calculated for C, H,NO Cl 268 Molecular weight found bypotentiometric determination in dimethylformamide with a 0.1 N solutionof tetra-n-butylammonium (TBA) hydroxide in an isopropanol/methanolmixture 272 EXAMPLE 12 ben- 0.015 mole (1.72 g) of o-chlorophenol isdissolved in 15 cc of a normal soda solution to which have been added ccof acetone. This iced solution is then added, with stirring, to 0.01mole (1.76 g) of 2-chloro quinonechloroimide partially dissolved in 8 ccof acetone. The stirring is continued for 30 minutes. Then 2 cc of a 2 Nsoda solution and 1.5 g of sodium chloride are added. The sodium salt ofthe above indophenol precipitates immediately in the form of mordoregreen crystals which are then filtered, washed with acetone and dried,yielding 1.7 g of chromatographically pure product. This salt is thendissolved in water. After acidification of the resulting solution withacetic acid, the above indophenol which has precipitated is filtered,washed with water and recrystallized in an acetonewater mixture. Afterdrying under vacuum, it melts at chloro)phenyl]-2,6-ditertiobutylbenzoquinoneimine is prepared as follows:

0.005 mole (1.03 g) of ditertiobutyl phenol is dis solved in 10 cc ofisopropanol to which have been added 10 cc of a normal potassiumsolution. This iced solution is added, with stirring, to 0.0075 mole(1.32 g) of 2-chloroquinone chloroimide partially dissolved in 6 cc ofisopropanol. Stirring is continued for 30 minutes and the reactionmixture is filtered to eliminate the 2- chloroquinonechloroimide whichhas not reacted. There are then added to the filtrate 20 cc of a 2 Npotassium solution and 2 g of potassium chloride in solution in 10 cc ofwater. The potassium salt of the above indophenol crystallizesimmediately. It is then filtered, washed initially with a little waterto which has been added potassium chloride and then with acetone. Theproduct is chromatographically pure.

EXAMPLE 14 The sodium salt of N-[(4'-hydroxy-3'-5'-dibromo)phenyl]2,6-dimethyl benzoquinoneimine is prepared as follows:

0.05 mole (6.1 g) of 2,6-dimethyl phenol is dissolved in 130 cc of a 2 Nsoda solution. To this solution, cooled in an ice-salt mixture, thereare added over a 45 minute period, with good stirring andsimultaneously, with the aid of a double funnel, on the one hand, 0.05mole (13.35 g) of 4-amino-2,6-dibromo phenol in solution in 200 cc of0.5 N hydrochloric solution and, on the other hand, 0.05 mole of 97%ammonium persulfate (11.75 g) in solution in 50 cc of water. Stirring iscontinued for 30 minutes while keeping the temperature in the vicinityof 0. The sodium salt of the above indophenol precipitates and isfiltered. After washing the same with a little water and then withacetone, the product is chromatographically pure.

EXAMPLE l5 The following hair dye composition is prepared:

Dye of Example 1 Ethyl alcohol, 96 titer Water, q.s.p.

Ammonia at 22Be, q.s.p.

0.05 g 25 g 100 g pH 8 This hair dye composition when applied for 20minutes to 95 percent naturally white hair, imparts thereto, afterrinsing and shampooing, a pearly beige shade with pink glints.

EXAMPLE 16 The following hair-setting lotion composition is prepared:

Dye of Example 1 COM macaque This hair-setting lotion when applied tobleached hair, imparts thereto a very luminous golden salmon 5 5 shade.

EXAMPLE 17 The following hair dye composition is prepared:

Dye of Example 2 0.1 g Ethyl alcohol. 96 titer 25 g Water, q.s.p. 100 gAmmonia at 22Be, q.s.p. pH 9.5

This hair dye composition when applied for 20 minutes to 95% naturallywhite hair, imparts thereto, after rinsing and shampooing a pearlytamarisk pink shade.

EXAMPLE 1 8 The following hair dye composition is prepared:

Dye of Example 2 0,025 g Dye of Example 4 0.2 g

Ethyl alcohol, 96 titer 40 g Butylglycol 5 g Water, q.s.p. 100 g Laurylalcohol oxyethylenated with Ammonia at 22Be, q.s.p. pH l 10.5 moles ofethylene oxide g Water, q.s.p. I00 g This hair dye composition whenapplied for 20 min- 5 h d utes to bleached hair, imparts thereto afterrinsing and t K S P Q when apphed f shampooing a pearly light blondshade with pink glints. u es 0 eac e lmparts thereto after rmsmg andshampooing a pearly pale pink shade.

EXAMPLE l9 0 7 EXAMPLE 24 The followlng hair-setting lotion is prepared:

The following hairsetting lotion is prepared:

Dye of Example 2 0.05 g

Vinyl acetate-crotonic acid copolymer Dye of Example 5 0.1 g (90% vinylacetate, 10% crotonic Vinyl acetate-crotonic acid copolymer acid,molecular weight 45,000 to (90% vinyl acetate, 10% crotonic 50,000) 2 gacid, molecular weight 45,000 to lsopropyl alcohol, 96 titer 50 g 2 gWater, q.s.p. 100 g Ethyl alcohol, 96 tlter 50 g Triethanolamine, q.s.p.pH 7 Water, l- -P- Ammonia at 22Be, q.s.p. p

This hair-setting lotion when applied to bleached Th t l 1' hair,imparts thereto a pearly salmon pink shade. 18 Se tmg when app tobleached hair, imparts thereto a pearly pink shade with mauve lints.EXAMPLE 20 g EXAMPLE 25 The following hair dye composition is prepared:The following hair dye composition iS prepared:

Dye of Example 3 0.4 g lsopropyl alcohol, 96 titer 40 g y of Example 6 0l g 3- a g Ethyl alcohol, 96 titer 40 g Ammonia at 22 Be, q.s.p. pH 7water q S p 100 g Ammonia at 22Be, q.s.p. pH [0 This hair y compositionwhen applied for 5 This hair dye composition when applied to bleachedUtes to 95 Percem naturally white hair, imparts thereto, hair for 20minutes, imparts thereto, after rinsing and after rinsing andshampooing, a pearly pink beige shampooing apearly pale ih Shade shade.

EXAMPLE 26 EXAMPLE 21 The following hair-setting lotion is prepared: Thefollowing hair-setting lotion is prepared:

Dye of Example 7 0.05 g

Vinyl acetate-crotonic acid copolymer y of Example 3 g (90% vinylacetate, 10% crotonic Vinyl acetate-crotonic acid copolymer acid,mo|ecu|ar weight 000 to (90% vinyl acetate, 10% crotonic 000 2 g acid,molecular weight 45,000 to 45 E h l l h l, 96 tit 50 g 50,000 a 2 2;Water, q.s.p. 100 g Ethyl alcohol, 96 titer 50 g Ammonia at 22Be, q.s.p.pH 9 Water, q.s.p. 100 g Triethanolamine, q.s.p. pH 7 This hair-settinglotion when applied to bleached This hair-setting lotion when applied tobleached 0 hair imparts thereto a golden apricot Shadeillallieimpartsthereto a very luminous salmon pink XA LE 7 The following hair dyecomposition is prepared:

EXAMPLE 22 The following hair-setting lotion is prepared: Dye of Example3 0.] g Nitroorthophenylenediamine 0.025 g N-[ (4'-amino-3,5'-dimethyl-2'-methoxy) hen l -2,6-dimeth lbenzo uinoney of Example 3901 g i mine I y q t 0.05 g Vinyl acetate-crotonic acid copolymer Ethy|alcohol, 9 m 25 g in Example 2l 2 g Ammonia at 22Be, q.s.p. pH 9 Ethylalcohol, 96 titer 50 g Water, qsp. g Trietlmnolamimav q ,p pH 7 Thishair dye composltlon when applied for 20 mmutes to 95 percent naturallywhite hair, imparts thereto, This hair-setting lotion when applied tobleached after rinsing and shampooing, a golden light bronze hair,imparts thereto a pink champagne shade. shade.

EXAMPLE 23 EXAMPLE 28 The following hair dye composition is prepared:The following hair dye composition is prepared:

y of Example 2 g This hair-dye composition when applied for 20 min-N-[4-amino-3 ',5 '-dimethyl-2-methoxy) phenyn 2 immethyl benzoquinoneutes to bleached hair, imparts thereto, after rinsing and imine 0.08 gshampooing, a very luminous intense violet pink color- N-[(6'-hydroxy-l'-oxa-4'-aza-l ,2,3, i

4-tetrahydro)-7-naphthyll-3-methoxy benzoquinonediimine monohydrate 0.16g This same halr-dye composltlon when applied for 20 56 alcohol 38 gminutes to 95 percent naturally white hair, imparts i g zg g pH thereto,after rlnslng and shampooing, a pearly pink beige shade. This hair dyecomposition when applied for 20 minutes to 95 percent naturally whitehair, imparts thereto, EXAMPLE 33 after rinsin and sham ooin a li htsilver bluish ra Coloration? p g g y g y The following halr-settlnglotion is prepared:

EXAMPLE 29 lndophenol of Example 9 in the form of its sodium salt 0.025g The followlng halr-setting lot1on ls prepared: Vinyl acetatecrotonicacid copolymer (90% vinyl acetate, 10% crotonic acid, molecular weight45,000 to 50,000) 2 s y of Example 4 0-087 g Ethyl alcohol, 96" titer 50g Nltrometaphenylen edlamlr le I 0.025 g water, qlsp. 0 g7-dlethylamlno-3-dlmethyllmlno-3H- Triethanolamine, pH 75 phenoxazlneperchlorate 0.012 g Vinyl acetate-crotonic acid copolymer (99% vinylacetate, l0% crotonic Thls halr-setting lotion when applied to bleachedg% g wegh45000m 2g hair, imparts thereto a very light pearly pink beigeEthyl alcohol, 96 titer 50 g Shld. Water, q.s.p. 100 g Triethanolamine,q.s.p. pH 7 r EXAMPLE 34 T i hair-Setting lotion when applied tobleached The following hair dye composition is prepared: halr, lmpartsthereto an ash gray shade.

ldh lfE llO'thf rl op eno o xampe m e orm EXAMPLE 30 of its sodium salt0.15 g W t 100 The following hair dye composltlon 15 prepared: a er q Sp g This hair dye composition, which has a pH of 9.5, lndophenol fExample H 025 g when applied for 20 minutes to 95 percent naturallyEthyl alcohol, 96 titer 40 g white hair, imparts thereto, after rinsingand shampoo- Water, q.s.p. 100 g d l Ammonia at 22Be, q.s.p, pH 9 arosewoo CO ormg 4O EXAMPLE 35 Thls dye coinposltion when apphed to 9 pepThe following hair-dye composition is prepared: cent naturally whltehalr for 20 minutes, lmparts thereto, after rinsing and shampooing, asilver gray shade. lndophenol of Example 8 0.1 g This same hair dyecomposition, when applied to mlg py alcohol mar 38 g I, .S. bleachedhalr for 5 minutes, lmparts thereto after rlnsa 22036, pH ing andshampooing, a silver light blue shade.

This hair dye composition when applied for 20 min- EXAMPLE 31 utes to 95percent naturally white hair, imparts thereto, after rinsin and shamooin ,a earl ash blond color- The following hair dye composltlon lsprepared: ing g p g p y lndophenol of Example 12 in the form of EXAMPLE36 its sodium salt 0.1 g Water, q.s.p. 100 g The following hair dyecomposltlon ls prepared: Ammonia at 22Be. q.s.p. pH 10 This hair dyecomposition when applied for 10 minlndophenol of Example 9 in the formof its utes to bleached hair, imparts thereto after rinsing and s gater,q.s.p. 100 g shampoolng, a turquolse blue colorlng.

This hair dye composition, which has a pH of 9, when EXAMPLE 32 appliedfor 20 minutes to bleached hair, imparts The following hair dyecomposition is prepared: thereto after "nsing and Shampoomg, a P yglycme shade. t 6 This same hair dye composition, when applied for 20 qp p of Example 8 in the form minutes to percent naturally white hair,imparts 3632: 229: Salt gb thereto, after rinsing and shampooing, amauve irides- The pH of this hair dye composition is 9.5. cent beigecoloring.

17 EXAMPLE 37 The following hair-setting lotion is prepared:

Dye of Example 7 in the form of its a This hair-setting lotion whenapplied to 95% naturally white hair, imparts thereto a pink beige shade.

EXAMPLE 38 The following hair-setting lotion is prepared:

Dye of Example 13 in the form of its potassium salt 0.2 g Vinyl acetatecrotonic acid copolymer (as in Example 33) 2 g Ethyl alcohol, 96 titer40 g Water. q.s,p. 100 g Triethanolamine, q.s.p. pH 7.5

This hair-setting lotion when applied to 95% naturally white hair,imparts thereto a very luminous copper blond shade.

EXAMPLE 39 The following hair dye composition is prepared:

Dye of Example 14 in the form of its sodium salt 0.4 g Water, q.s.p. 100g Ammonia at 22Be, qsp. pH 9.5

This hair dye composition when applied for 20 minutes to 95 percentnaturally white hair, imparts thereto, after rinsing and shampooing, asilver gray blue shade.

What is claimed is:

1. A dye composition for human hair comprising a solution in a solventselected from the group consisting of water and an aqueous solution of alower alkanol selected from the group consisting of ethanol andisopropanol wherein said lower alkanol is present in amounts of about 20to 70 percent by weight of said composition of an indophenol selectedfrom the group consisting of a. an indophenol of the formula 18 3 1 3*a; HO-- l 1 ,/-o

Ru R2 wherein R R R and R each independently, represent a memberselected from the group consisting of halogen selected from the groupconsisting of chlorine and bromine, hydrogen, lower alkoxy having l-4carbon atoms and lower alkyl having 1-4 carbon atoms with the provisothat at least one of R R R and R is said halogen; and

b. an alkaline salt of the indophenol in (a) selected from the groupconsisting of the ammonium, sodium and potassium salt thereof; saidindophenol being present in amounts of 0.002 to 2 percent by weight ofsaid composition.

2. The composition of claim 1 having a pH between 4 and l l.

3. The composition of claim 1 which also includes a glycol selected fromthe group consisting of propylene glycol and butyl glycol in amounts ofabout l-6 percent by weight of said composition.

4. The composition of claim 1 which also includes a film-formingcosmetic resin in amounts of l to 3 percent by weight of saidcomposition, said film forming resin being selected from the groupconsisting of polyvinylpyrrolidone having a molecular weight rangingfrom about 10,000 to 200,000, copolymer of crotonic acid and vinylacetate having a molecular weight ranging from about 10,000 to 70,000copolymer of vinylpyrrolidone and vinyl acetate wherein the ratio of VPto VA ranges between 50-70:5030, said copolymer having a molecularweight ranging from about 30,000 to 200,000 and maleic anhydride-butylvinyl ether copolymer, a 1 percent solution of which inmethylethylketone has a viscosity of 0.1-3.5 cps at 25C.

5. The composition of claim 4 having a pH between 5 and 8.

6. A process of dyeing human hair comprising impregnating the hair witha dye composition as defined in claim 1, permitting said composition toremain in contact with said hair for a period of 3 to 30 minutes,rinsing said hair with water and drying said hair.

7. A process for setting human hair which comprises impregnating wethair with a composition according to claim 4 and then rolling said hairup on curlers and drying said hair.

1. A DYE COMPOSITION FOR HUMAN HAIR COMPRISING A SOLUTION IN A SOLVENTSELECTED FROM THE GROUP CONSISTING OF WATER AND AN AQUEOUS SOLUTION OF ALOWER ALKANOL SELECTED FROM THE GROUP CONSISTING OF ETHANOL ANDISOPROPANOL WHEREIN SAID LOWER ALKANOL IS PRESENT IN AMOUNTS OF ABOUT 20TO 70 PERCENT BY WEIGHT OF SAID COMPOSITION OF AN INDOPHENOL SELECTEDFROM THE GROUP CONSISTING OF A. AN INDOPHENOL OF THE FORMULA4-((4-(O=),R1,R2-CYCLOHEXA-2,5-DIEN-4-YLIDENE)=N-), R3,R4-PHENOL WHEREINR1, R2, R3 AND R4, EACH INDEPENDENTLY, REPRESENT A MEMBER SELECTED FROMTHE GROUP CONSISTING OF HALOGEN SELECTED FROM THE GROUP CONSISTING OFCHLORINE AND BROMINE, HYDROGEN, LOWER ALKOXY HAVING 1-4 CARBON ATOMS ANDLOWER ALKYL HAVING 1-4 CARBON ATOMS WITH THE PROVISO THAT AT LEAST ONEOF R1, R2, R3 AND R4 IS SAID HALOGEN, AND B. AN ALKALINE SALT OF THEINDOPHENOL IN (A) SELECTED FROM THE GROUP CONSISTING OF THE AMMONIUM,SODIUM AND POTASSIUM SALT THEREOF, SAID INDOPHENOL BEING PRESENT INAMOUNTS OF 0.002 TO 2 PERCENT BY WEIGHT OF SAID COMPOSITION.
 2. Thecomposition of claim 1 having a pH between 4 and
 11. 3. The compositionof claim 1 which also includes a glycol selected from the groupconsisting of propylene glycol and butyl glycol in amounts of about 1-6percent by weight of said composition.
 4. The composition of claim 1which also includes a film-forming cosmetic resin in amounts of 1 to 3percent by weight of said composition, said film forming resin beingselected from the group consisting of polyvinylpyrrolidone having amolecular weight ranging from about 10,000 to 200,000, copolymer ofcrotonic acid and vinyl acetate having a molecular weight ranging fromabout 10,000 to 70,000, copolymer of vinylpyrrolidone and vinyl acetatewherein the ratio of VP to VA ranges between 50-70:50-30, said copolymerhaving a molecular weight ranging from about 30,000 to 200,000 andmaleic anhydride-butyl vinyl ether copolymer, a 1 percent solution ofwhich in methylethylketone has a viscosity of 0.1-3.5 cps at 25*C. 5.The composition of claim 4 having a pH between 5 and
 8. 6. A process ofdyeing human hair comprising impregnating the hair with a dyecomposition as defined in claim 1, permitting said composition to remainin contact with said hair for a period of 3 to 30 minutes, rinsing saidhair with water and drying said hair.
 7. A process for setting humanhair which comprises impregnating wet hair with a composition accordingto claim 4 and then rolling said hair up on curlers and drying saidhair.